THE REACTION OF TRIPHENYLPHOSPRINEBX'RYLENES WITH LITHIUM ALUMINUM RYDRIDE Martin Saunders and Gracie Burchman~ Sterling ChemistryLaboratory,Yale University,New

Haven, Corm.** (Received26 January 1959)

ALTHOUGH triphenylphoaphineacylmethylenea have been known for some time,' Wittig'e recent preparationof the simpler analoge has been of interest because of their eynthetioutility.2 We wish to report a new reaction which these compoundsundergo on treatmentwith lithium aluminum hydride, When the triphenylphosphinemethylenee, (C6H5)3P-CHR: (I) R=H, (II) R= COCH3, (III) R-COC6H5, 3 (IV) R=COC(CH3)2COCH(CH3)2

United States Public Health PredoctoralFellow of the National Instituteof Arthritis and Metabolic Diseases, 1957 - 59. Yale University,New Haven, Connecticut. A. Miohaelie and E. Kohler, Ber. Dtrrah. Chem. Ges, 22,

** Contribution No. 1518 from the Sterling Chemistry Laboratory,

1566 (1899). G. Wittig and U. Bchollkopf,Ber. Dteoh. Chem. Gee, :I, 1318
(1954)1G. Wittig, Exwrientia 22, 41 (1956); G. Wittig, Azwer. Chem, pi, 505 (1956); F. Ramire% and S. Dershowltz, J. Org. memm, 22, 41 (1957). Preparationand structuralinformationare desoribed in Ph. D. Theeie of P. Saunders,Harvard University (1956).

Triphenylphosphlneue~lenos

ware rtlrred with exoessreagentin either-tetrahydrofuran, produotr were obtained on hydrolysis in whlohhydrogen had been addedto the methylone carbonand whiohhad lootbensene. (I) gave a liquidphosphine uhiohfieldeddimethyldiphenylphosphonfun Iodideupon treatment Seth methyliodide(2meldf m.p. 249.5-2510,

1it.4 241.Found:C, 48.9fH, 5.OfP, 9.2. Cal% for C14E16PI 8 c, 49.11

B, 4.7f

P, 9.d). Illu phosphiner readilyoxldised on standing In air to

orysblllnephosphine oxides. (II)6aw (C6%,)2P(0)cH2CocB5 (ltieldf m.p. 127-1290 A, (C-O), 8.4W (P +-O -). Found:C, 70.288, 6.31 P, 12.0.Clfi502P reqdrea C, 69.88H, 5.91P, 12.0%). (III)@m
L5.96 C&70$ (C-O), mamm

5.84

(C6E5&P(0)CI$COC6H5 (46 jieldf8.~. 140-140.5.

(P+-O-1.

8.47~

Found:C, 74.98H, 5.61P, 10.0.

C# 75.OfHe 5.45P, 9.796). (54 k rI*ldf 8.47 v @+

(Iv)eve (c6E5)2p(0)~c~(~~)2~OE~(~)2
Y5 - Y7.5O. x, 2.96 (OH), 5.87 (C - 01,

ma.

o- 1.

C, 70.6rE, 7.6 Found:C, 70.7, He 7.61 P, 8.9. C21&$3P requlror P, 8.6 $>. The 18olatlon of ketonioproduotr afterreaotlon In the preaenao In tenseof an enolate salt of excessLiAlE is most readilylrplloable 4 uhiohle reslrtant to further attaoh.Suohan enolate might be formedby eitherattaahof the LUllI on the phony1groupproduoing bensona dlreot3J or addition to the phosphorour atom givinga pentavalent Intermediate whloh aan lose bbnsbnb phenMwhorow5
in

a mannerrlmllar to thelorr ofbiphenylfrompenta-

4 A. Hiohaells and A. Link, Llebinr Aan% gOJ, 193 (1891). 5 0. Wittlgand 0. Coirsler, Jlebl&sAnn, a, 44 (1953).